CN104458678B - For photochemistry or the measurement film of amperometric sensor - Google Patents

For photochemistry or the measurement film of amperometric sensor Download PDF

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Publication number
CN104458678B
CN104458678B CN201410466339.0A CN201410466339A CN104458678B CN 104458678 B CN104458678 B CN 104458678B CN 201410466339 A CN201410466339 A CN 201410466339A CN 104458678 B CN104458678 B CN 104458678B
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sensor
matrix
measurement film
film
layer
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CN201410466339.0A
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Chinese (zh)
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CN104458678A (en
Inventor
克里斯蒂安·范泽洛
安德烈亚斯·罗贝特
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恩德莱斯和豪瑟尔分析仪表两合公司
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Publication of CN104458678A publication Critical patent/CN104458678A/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electro-chemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electro-chemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/40Semi-permeable membranes or partitions
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using infra-red, visible or ultra-violet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using infra-red, visible or ultra-violet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using infra-red, visible or ultra-violet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/775Indicator and selective membrane
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using infra-red, visible or ultra-violet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769Measurement method of reaction-produced change in sensor
    • G01N2021/7786Fluorescence
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using infra-red, visible or ultra-violet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electro-chemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electro-chemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/404Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors

Abstract

The present invention relates to a kind of measurement films (8) being used for photochemistry or amperometric sensor, and for determining or monitoring the analyte (12) being located in medium, which includes:Base material (2) and sensor element (3), the sensor element (3) has at least one functional layer (4) with sensor dedicated substances (18), wherein sensor element (3) is fully inserted into matrix (9), and its mesostroma (9) is by being that permeable material is constituted to the analyte (12) at least in the part towards the medium (11) and the adjacent sensor element (3).

Description

For photochemistry or the measurement film of amperometric sensor

Technical field

The present invention relates to a kind of measurement films being used for photochemistry or amperometric sensor, are used for using sensor element come really Fixed or monitoring is located at the analyte in medium, which includes:At least one functional layer with sensor dedicated substances;With And base material.In addition, the present invention relates to a kind of sensor cap and photochemistry or amperometric sensors.

Background technology

Such as the spectrochemical analysis object sensor of lambda sensor depend on for example carry in the polymer matrix it is organic Toner analyte induction fluorescent quenching or shine principle is quenched.In general, being suitable for polymer/coloring of scheduled analyte Agent composition is applied to as solid film in the substrate of such as sheet glass or optical fiber.

Become known for determining and/or monitoring the analyte being included in flow liquid process medium from 2005/100957 A1 of WO Device.The known devices include with the sensor for measuring film, with porous support structure.It is embedded in support construction The luminescent substance of contact process medium.Additionally provide transmitter unit and receiving unit, the wherein radiation of transmitter unit emission measurement simultaneously And excitation luminescent substance makes it emit luminous radiation, and wherein receiving unit detects the luminous radiation correspondingly generated.Control The concentration for the analyte of luminous radiation of the system/assessment unit based on luminescent substance being quenched in determination process medium respectively, part Pressure/pressure.Term shines to refer to generates optical radiation when being transformed into basic status from excited state in substance.

Equally, 2003/0068827 A1 of US describe optical sensor.Although the supporting layer and hair of usual form stable The film-forming material of light is used together, but in the U. S. application, describes such a solution, in this case, Support construction is embedded in the permeable polymer of correspondence analysis object/colorant matrix.The technology and the hair applied in the carrier Stimulative substance is compared to two advantages of offer:On the one hand, the scattering that the matrix being embedded in film causes to measure radiation in film increase and Therefore luminous radiation increases;On the other hand, the stability of film due to fixed support construction but it is larger.Especially, matrix It is glass fiber filter, absorbs luminescent substance.Cellulose, cellulose acetate and nylon are the other materials for matrix. In order to manufacture film, support construction is dipped into luminescent substance, and excessive luminescent substance is then dried so that luminescent substance is made Each fiber is entangled for coating.Space between each fiber keeps no luminescent substance.

Moreover, from the known luminescent substance embedded in silicone of United States Patent (USP) 5,057,277.For this purpose, for stable purpose, Silicone is mixed with packing material.Packing material is, for example, silicate.In addition, luminescent substance is introduced into silicone.The structure is therefore Separately include the matrix and support construction of silicone and silicate.

Become known for determining the especially optical sensor of the analyte of oxygen and for manufacturing from 100 51 220 A1 of DE Method.Known optical sensor includes the biosensor matrix substantially formed by fluoropolymer.Biosensor matrix includes Luminous indication, it includes the metal complexes of ruthenium, rhenium, rhodium or iridium and at least one portion fluorinated ligands.Biosensor matrix is real It applies as foil-like and setting matcoveredn.Protective layer does not include hair preferably by material manufacture identical with biosensor matrix Optical indicator.In this way, it is therefore prevented that being in direct contact between the fringe region and measurement matrix of biosensor matrix.It prevents by process The mechanical damage of biosensor matrix caused by abrasive particle in medium.

The laminar flow layer structure of such as those described above is suitable for photoelectric sensor and is referred to as measuring film or sensor Point (sensor spot).These are directly sold to such as biotechnology company and food company or they are supplied to Sensor manufacturer for manufacturing so-called sensor cap.Partly, film and sensor points are measured also by respectively by sensing Device company directly manufactures and sells.

In order to manufacture the optical measurement film for industrial automation technology, in general, using the permeable film of analyte, it is right Heated alkaline solution and acid have certain chemoresistance.Therefore, it in order to clean sensor, is applied in the food industry about Such as sodium hydroxide or potassium hydroxide solution with about pH13 to the pH value of pH14 ranges at a temperature of 40 DEG C to 90 DEG C ranges Alkaline solution or strong acid that pH value range is about pH0 to pH1.In periodic cyclic, sensor, especially sensor cap, It is exposed to these extreme conditions.It is stopped certain time in aggressivity cleaning medium in sensor and (depends on cap to design and sense Equipment material) after, the delamination or independent particle that may undergo the individual course for measuring film are dissolved out from measurement film.It is broken as this It is bad as a result, sensor loses its ability to work.In addition to this, the membrane part measuring contamination solution being dissolved out.

It is suitable for optics and amperometric sensor, the layer knot for measuring film by a variety of materials applied in automatic technology Structure is constituted, and is worked the required different performance of ability with sensor.Thus, for example, the first layer of layer structure provides choosing Selecting property analyte permeation, second layer concern measures the chemistry and/or mechanical stability of film, and third layer is in corresponding excitation When emit certain wavelength and analyte particular phase angle fluorescence signal or phosphorescent signal or its absorb light.With corresponding The sensor for measuring film is produced and sold by applicant.

What the known bedded structure of measurement film was not without problems.As already mentioned previously, it may happen that individually Layer can the delamination after certain residence time, especially the high temperature of cleaning medium (>40 DEG C) and extreme ph values (pH< 2, pH>12) under.The usual adjoint substance of cleaning medium, such as oxide isolation of ethyl alcohol or such as hypochlorite can be into one Step accelerates to measure the aging of film.They can lead to each layer of delamination or destruction of layer structure, because they are to pledging love Subversive gas can be discharged in shape.In this way, the known bedded structure of functional layer can cause to measure the deterioration of film and lead It causes membrane part to be dissolved into measure in medium.

Invention content

The object of the present invention is to provide the measurement film of photoelectricity or amperometric sensor for industrial automation technology and biographies Sensor cap, wherein sensor maintain its functionality under high request environmental condition.

The purpose is realized by a kind of, be used to determine or monitored for the measurement film of photochemistry or amperometric sensor Analyte in medium is made of wherein measuring film base material and sensor element, and sensor element has with biography At least one functional layer of sensor dedicated substances, wherein sensor element are fully inserted into matrix, and its mesostroma is by extremely Few is that permeable material is constituted to analyte in the part towards medium and adjacent sensor element.Term " analyte " closes In present invention be directed to that being located at any type of ion or gas in liquid.

The present invention measurement film first embodiment in, matrix at least one of its surface region with substrate material Expect physically or is coupled chemically.Usual way is for connecting host material and base material.

Alternative embodiment provides, moreover, base material is at least partially embedded in matrix, and in given situation In be permeable to analyte.In this way, sensor film can be stablized with version and firm (robust).According to base The embodiment of the material of matter measures film and may be coupled in sensor cap, without supplementing sealing element.

The preferred solution of the measurement film of the present invention provides, and sensor element has layer structure and by least two work( Ergosphere is constituted, wherein one in functional layer includes sensor dedicated substances, or is made of sensor dedicated substances.

In the advantageous further development of the measurement film of the present invention, sensor dedicated substances are selectively to analyte It is permeable.In this case, moreover, host material is embodied as permeable analyte at least partly.Alternatively, it provides Sensor dedicated substances are formed in this way:So that it changes it chemically or physically in performance by being contacted with analyte At least one, wherein change be detectable followed by corresponding detector cell.

Preferably, the material of matrix be done so as to its relative to the medium and/or cleaning medium of measurement be chemically and Physically stablize --- therefore it is in high measurement repellence.For example, the material of matrix can be silicone.Moreover, making manufacture base What the material of matter was suitable for being advantageously applied in field of food.Especially in this respect, FDA guides should be followed.

In the advantageous further development of the measurement film of the present invention, base material is preferably by one kind in following material It constitutes:Glass, ceramics, polymer, metallo-organic compound, metal organic frame and zeolite.Certainly, base material is also acted as Be composition, be especially made of at least two in previous materials.In order to increase the form stable for measuring film, upper In the situation for stating the two in solution, the supportive grid in embedded matrix can also be provided and/or keep grid.

If it is desired to using the measurement film of the present invention in the situation of amperometric sensor, then providing base material has Cavity in the region of placement sensor professional component.Such as the end regions of pH electrodes extend in cavity.It is preferred that Ground, in addition, above-mentioned holding grid is disposed directly upon before cathode.According to the present invention, which for example can be that current mode passes The compound electrode of sensor (such as chloride) and one or more optical sensors (such as pH or DO sensors).In the situation Under, the film is by gas-selectively permeable element and the sensor activated by ion (such as pH) or gas (such as DO) Professional component forms.

The invention further relates to a kind of sensor caps, by cylindrical housings and the present invention being arranged in the end regions of shell Sensor film, that is, one in the sensor film composition.

For stability sensor film, sensor cap preferably has the lid with central opening.Lid is fixed on cylinder In the end regions of shape shell, such as pass through screw thread or clip mechanism.Lid is done so as to it in the marginal zone towards medium The surface of sensor film is covered in domain.

The embodiment of sensor of the invention cap provides, and sensor film is airtightly arranged in cylindrical housings.

In addition, the solution of the present invention is related to the current mode or light for measuring film and/or sensor cap with the present invention Chemical sensor.The basic element of character of Optochemical sensor is transmitter unit, receiving unit and control/assessment unit, has such as been carried It arrives.The variable that the specific embodiment of individual sensor element finally always depends on actually measuring is (thus, for example, solution In oxygen, nitrogen, carbon dioxide or chlorine can carry out qualitatively or quantitatively determine) and be adapted to determine that the sensors of material variables Proprietary material.According to application, sensor proprietary material is phosphorescent colorant, color indicator or the choosing of the analyte to be determined The permeable substance in selecting property ground.

Briefly, the purpose of the present invention is achieved by the features that, including:Sensor member with sensor dedicated substances Part, correspondingly sensor dedicated substances are disposed in sandwich.Sandwich --- especially with it is front and/or lateral Covering --- such as cap stably measured film in combination so that the rupture of membrane part is correspondingly dissolved extremely difficult or hindered Only.Sensor dedicated substances can be selectively permeable substance or colorant.Advantageously, it is incorporated to the base of sensor element The surface physics of matter and sensor element or be coupled chemically or combine.For this purpose, all sides well known by persons skilled in the art Method can be applied.By measuring the sandwich of film, realize in face of common detergents, such as phosphoric acid, nitric acid, hydroxide The stability of longer time when sodium, sodium hypochlorite, sulfuric acid, monoxone or hydrogen peroxide.By means of the present invention, greatly reduce The danger of film relevant sensor downtime.It tests it has been confirmed that sensor of the invention cap is in 90 DEG C of hot sodium hydroxides (5%) it optically and is mechanically stood intact by holding after more than 50 times cleaning circulations (30 minutes) in and is also airtight With it is liquid-tight.

Description of the drawings

It is now based on attached drawing and the present invention is explained in greater detail, the figure in attached drawing shows as follows:

Fig. 1 a are across changed from the prior art and fixed measurement film for determining analyte in the housing Longitudinal section,

Fig. 1 b are the measurement films of Fig. 1 a after a large amount of cleaning circulation,

Fig. 2 a are the longitudinal sections of the first embodiment of the measurement film across the fixed present invention in the housing,

Fig. 2 b are across the longitudinal section of sensor cap, and in this case, the measurement film shown in Fig. 2 a is fixed via lid In the housing,

Fig. 2 c are in this case, the second of the measurement film of the present invention have been used to implement across the longitudinal section of sensor cap Example, and

Fig. 2 d are across the longitudinal section of sensor cap, and in this case, the third for applying the measurement film of the present invention is implemented Example,

Fig. 2 e are across the longitudinal section of sensor cap, and in this case, apply the measurement film of the present invention the 4th implements Example,

Fig. 3 is the perspective view across the longitudinal section of the preferred sensor cap of the present invention, and

Fig. 3 a are across the cross section of Fig. 3 sensor elements with such as optical point.

Specific implementation mode

Fig. 1 a are shown across the longitudinal section of sensor cap 1 known in the art, are made of cylindrical housings 6, should Cylindrical housings 6 pass through for determining that the measurement film 8 of analyte 12 is closed in end regions towards medium 11.For example, it is to be determined or Analyte 12 to be monitored can be included in ion or gas in medium 11.The measurement film 8 shown in Fig. 1 a is from existing skill Art is changed.

This is made of sensor element 3 and base material 2.Sensor element 3 may be embodied as making it suitable for light Electrical measurement or current measurement.In addition, film 9 can be incorporated into equipped with installable optical element (LED, photodiode, optics Waveguide etc.) reactor transparent wall in.Known sensor element 3 is the layer structure formed by multiple and different functional layers 4 13, wherein functional layer 4 is matched with specific application.Especially, individual functional layer 4 is formed so that they rise corresponding to sensor The different demands of the ability of effect.For example, the first functional layer 4 of layer structure 13 for example provides selective analyte permeation, the The concern of two functional layers 4 measures the chemistry and/or mechanical stability of film 8, and third functional layer 4 is distinguished in corresponding excitation situation Emit the luminous and fluorescence or phosphorescent signal or its absorption light of certain wavelength and analyte particular phase angle.Therefore, third work( 4 carry sensors dedicated substances 18 of ergosphere.In the situation of photoelectric sensor, sensor dedicated substances 18 are especially depending upon medium Analyte 12 to be determined and monitoring in 11.

What the layer structure 13 with its bedded structure was not without problems.As already mentioned previously, it may happen that Layer structure 13 the delamination after certain residence time in cleaning medium of individual functional layer 4, especially high temperature (>40 DEG C) Situation and extreme ph values (pH<2, pH>12) under.This generation is shown in Figure 1b.The individual functional layer 4 of layer structure 13 is once The sensor of delamination, wherein integral measuring film 8 is just out of order.

In addition to this it is the usual substance with cleaning medium, such as oxide isolation of ethyl alcohol or such as hypochlorite can be with Accelerate the aging of measurement film 8.For example, subversive gas can measure the part of film known to substance release, dissolving, by This loses its physical integrity.In addition, the part of the measurement film 8 of dissolving causes medium 11 to pollute, this cannot be tolerated, especially In the situation about the application of food production.

Fig. 2 a show the first embodiment of the sensor cap 1 of the measurement film 8 with the present invention.Film is measured to be arranged so that It is in the end-enclosed conical shell 6 towards medium 11.Measurement film 8 is done so as to it and is adapted for use in determining or monitoring position The Optochemical sensor of analyte in medium 12.According to the present invention, film 8 is measured by 3 structure of base material 2 and sensor element At it includes sensor dedicated substances 18 that sensor element 3, which has at least one functional layer 4, at least one functional layer 4,.Sensing Device element 3 is fully inserted into matrix 9.Matrix 9 is made of the material of such as silicone, at least towards medium 11 and adjoining It is permeable to analyte 12 in the part of sensor element 3.One in shown situation in its surface region of matrix 9 In physically or chemically connect with base material 2.Be preferably used for matrix 9 is relative to medium 11 and/or common clear Clean media chemistry and physically stable material.In addition, the material of matrix 9 is selected such that it is suitable in field of food In application.

For example, base material 2 can be glass, ceramics, polymer, metallo-organic compound or zeolite.In addition, substrate material Material 2 can have hybrid architecture, be preferably made of at least two in previous materials.Base material 2 gives the present invention 8 necessary stability of sensor film.According to the present invention, at least sensing of the functional layer 4 with its different foil-like or stratiform Device element 3 is embedded in matrix 9 to form sandwich.In addition, base material 2 can regionally connect with matrix 9 or It is embedded in matrix 9.Sandwich is to measure film 8 to provide high stability.

In one embodiment, sensor element 3 includes the multilayer system of at least two sensor elements 21.Sensor 21 Include polymeric layer with embedded pigment (pigment), shielding layer (shade layer), for preventing optical sensor The layer of photobleaching (photo bleaching), the infiltrative layer for increaseing or decreasing analyte 12, supporting layer, retaining layer, To the selectively permeable layer, and/or the layer for buffered pH value of analyte 12.

Fig. 2 b show that, across the longitudinal section of sensor cap 1, above-described embodiment of measurement film 8 of the invention is integrated into sensing In device cap 1.In the situation of the embodiment, measure film 8 by by means of the terminal for supplementing cap type and/or lateral covering by Addedly reinforce, supplements the herein also called lid of cap.In illustrated case, therefore, supplement cap is opened with screw thread and center The lid 5 of mouth 15 is formulated in size so that measuring film and is capped only in the fringe region 10 of lid 5.The design to disappear Except the component of measurement film 8, correspondingly 4 delamination of individual functional layer is extremely difficult, correspondingly entirely prevented these situations.At this Advantage in the situation of embodiment be by corresponding selection lid 5 and measure film 8 the outer surface towards medium 11 between The material of matrix 9 in contact area, realizes good sealing function so that no medium 11 can be penetrated into circular cylindrical shell The inside of body 6.It can be omitted the other sealing for example via sealing ring 19,20 (see Fig. 3).

Fig. 2 c show across the longitudinal section of sensor cap 1, in this case, apply the of the measurement film 8 of the present invention Two embodiments.In the situation of the embodiment, sensor element 3 and also both base materials 2 are integrated into matrix 9 with completing In.Both components 2,3 are embedded in sandwich in matrix 9.In addition, in the situation of the embodiment --- similarly for example scheme In the situation of the embodiment shown in 2a, 2b and 2d --- supportive grid 14 can be provided and/or keep grid 17, give this The sensor film 8 of invention, the correspondingly other stability of sensor of the invention cap 1.As illustrated in fig. 2 c, matrix can also be with Substitute mode (displaced manner) is arranged into substrate.

Fig. 2 d are shown across the longitudinal section of sensor cap 1, illustrate the 3rd embodiment of the measurement film 8 of the present invention, It is particularly suitable for the use in amperometric sensor.The embodiment is very similar to the embodiment shown in Fig. 2 b, removes substrate Material 2 includes except cavity 7.By the cavity 7, make reference electrolyte closer to the sandwich of the present invention.In addition, keeping lattice Grid 17 and supportive grid 14, which are disposed in, to be measured in film 8.Keep grid 17 for mechanically stable and as in sensor cap 1 Barrier layer (barrier layer) on inside.The mechanically stable measurement film on the side opposite with medium 11 of supportive grid 14 8.In addition, advantageously, in this case, matrix 9 is performed simultaneously sealing element in the situation of embodiment shown in figure 2d Function.Such as the material by selection matrix 9 appropriate, it is convenient to omit sealing ring.

Fig. 2 e are shown across the longitudinal section of sensor cap 1, are illustrated the fourth embodiment of the measurement film of the present invention, are shown Multi-embedding matrix is gone out.Sensor layer includes subbase matter 23, which includes pigment, microballoon and polymer.Subbase matter 23 It is embedded into transparent intermediary substrate 22, transparent intermediary substrate 22 prevents the radiation from medium 11 or from singlet oxygen from encroaching on (radial offense).Intermediary substrate 22 and subbase matter 23 are embedded in together with another protective layer of such as stabilized glass web Into already mentioned matrix 9.

In subbase matter 23, by intermediary substrate 22 and prevent machinery encroach on another matrix 9, analytic function layer 4 from Free radical (radical) gas and ion from medium 11 and photobleaching.Single matrix may include different hydrophobicity (hydrophobia)。

Fig. 3 shows the perspective view of the longitudinal section of the preferred form of the embodiment across sensor of the invention cap 1.Fig. 3 a Show the cross section of the sensor element 3 across Fig. 3.As described above, film 8 is measured according to embodiment and according to sensing The dedicated functional layer of device and be adapted for use in determine or monitoring be located at medium 11 in analyte 12 any Optochemical sensor Or any amperometric sensor.Preferably, idea of the invention is for the oxygenation measurement in aqueous solution.

It includes sensor element 3 to measure film 8, is usually made of multiple functional layers 4,4a.Basic training ergosphere 4 includes sensing Device dedicated substances 18.In addition, functional layer 4a is embodied as protective layer, the interference radiation from environment is absorbed at least partly.It is existing There is protective layer other known to technology that can be provided according to application.In addition, it includes base material 2 to measure film 8.

According to the present invention, in shown situation, sensor element 3 is fully inserted into matrix 9, and mesostroma 9 is by least 12 permeable material of analyte is constituted in the part towards medium 11 and adjacent sensor element 3.Matrix 9 is at it It physically or is coupled chemically with base material 2 in lower surface area.It has already mentioned above, base material 2 can also be partly Or it is fully inserted into matrix 9.Then, the material of matrix 9 must be at least in the part towards analyte 12 to analyte 12 It is permeable.

Film 8 is measured to be releasably fixed in shown situation in sensor cap 1.In order to make sensor cap 1 relative to Jie Matter 11 seals, and sealing ring 19,20 is provided in the upper edge region and lower edge margin 10 for measuring film 8, measures film 8 via this Sealing ring 19,20 resists lid 5 (the correspondingly shell 6) sealing of sensor (not displaying the details of).Preferably, the material of matrix 9 It is can be chosen such that with certain flexibility, to realize sealing function when being integrated into sensor cap 1.In given situation In, it then can be omitted one in two sealing elements 19,20 or the two even in sealing element 19,20.The situation shown in In, sensor cap 1 is engaged via screw thread with the shell 6 of sensor so that when needed sensor can by readily replaceable and/or Cleaning.

List of numerals

1 sensor cap

2 basal layers

3 sensor elements

4 functional layers

5 sensor covers

6 shells

7 cavitys

8 measure film

9 matrix

10 fringe regions

11 media

12 analytes

13 layers of structure

14 supportive grids

15 openings

16 end regions

17 keep grid

18 sensor dedicated substances

19 sealing elements/sealing ring

20 sealing elements/sealing ring

21 sensor elements

22 intermediary substrates

23 subbase matter

Claims (20)

1. a kind of measurement film for Optochemical sensor, for determining or monitoring liquid(11)
In analyte(12), the measurement film includes:Base material(2)And sensor element(3),
The sensor element(3)With with sensor dedicated substances(18)At least one function
Layer(4),
Wherein, the sensor element(3)It is fully inserted into matrix(9)In, and wherein,
The matrix(9)By at least towards the liquid(11)And the adjacent sensor element
(3)Part in the analyte(12)It is that permeable material is constituted, wherein described
Sensor element(3)With by least two functional layers(4)The layer structure of composition(13),
In, the functional layer(4)In one include the sensor dedicated substances(18).
2. according to the measurement film described in claim 1,
Wherein, the matrix(9)In one in its surface region with the base material(2)
Physically or it is coupled chemically.
3. according to the measurement film described in claim 1,
Wherein, the base material(2)It is at least partially embedded the matrix(9)In and
At least partly to the analyte(12)It is permeable.
4. according to the measurement film described in claim 1,
Wherein, the sensor dedicated substances(18)It is done so as to selectively to described
Analyte(12)It is permeable.
5. according to the measurement film described in claim 1,
Wherein, the sensor dedicated substances(18)Be done so as to its by with the analysis
Object(12)It contacts and changes its chemically or physically at least one of performance, wherein is described to change
Change is detectable.
6. according to the measurement film described in claim 1,
Wherein, it is used as the matrix(9)Material be relative to measured medium(11)With
/ or cleaning medium be chemically and physically stable material.
7. the measurement film according to claim 1 or 6,
Wherein, it is used as the matrix(9)Material be suitable for the material applied in field of food
Material.
8. according to the measurement film described in claim 1,2 or 3,
Wherein, the base material(2)Preferably it is made of a kind of in following material:Glass,
Ceramics, polymer, metallo-organic compound and zeolite, or
Wherein, the base material(2)With mixed structure and preferably by previous materials
At least two compositions.
9. according to the measurement film described in claim 2,
Wherein, the base material(2)It is at least partially embedded the matrix(9)In and
To the analyte(12)It is permeable.
10. according to the measurement film described in claim 1,2 or 3,
Wherein, the base material(2)Arranging the sensor element(3)Region in
With cavity(7).
11. according to the measurement film described in preceding claims 1,2 or 3,
Wherein, the embedded matrix of setting(9)In supportive grid(15)And/or keep lattice
Grid(17).
12. according to the measurement film described in preceding claims 1,2 or 3,
Wherein, the sensor element(3)It includes at least two sensor elements to be(21)'s
Multilayer system.
13. according to the measurement film described in claim 12,
Wherein, the sensor element(21)Include polymeric layer with embedded pigment,
Shielding layer, the layer for preventing optical sensor photobleaching, for increaseing or decreasing analyte(12)
Infiltrative layer, supporting layer, retaining layer, to analyte(12)It is selectively permeable
Layer, and/or the layer for buffering pH value.
14. according to the measurement film described in claim 13,
Wherein, including at least two sensor elements(21)The multilayer system be embedded into son
Matrix(23), and the subbase matter(23)It is embedded into intermediary substrate(22), and the subbase
Matter(23)And/or the intermediary substrate(22)It is embedded into the matrix(9).
15. the measurement film according to preceding claims 14,
Wherein, matrix(9), subbase matter(23)And/or intermediary substrate(22)Matrix in
At least one includes having different hydrophobic materials.
16. the measurement film according to preceding claims 15,
Wherein, matrix(9), subbase matter(23)And/or intermediary substrate(22)Matrix in
At least one includes having different hydrophobic materials, described to have different hydrophobic materials
Material is Teflon or sol-gel.
17. a kind of sensor cap, including cylindrical housings(6)And it is arranged in the shell(6)
End regions(16)In measurement film(8), the measurement film(8)It is such as claim 1-16
In any one described in measurement film(8).
18. according to the sensor cap described in claim 17, wherein provided with being opened with center
Mouthful(15)Lid, the lid is can be fixed on the cylindrical housings(6)End region
Domain(16)In, and towards medium(11)Fringe region(10)The middle covering survey
Measure film(8)Surface.
19. the sensor cap according to claim 17 or 18,
Wherein, the measurement film(8)Airtightly it is arranged in the sensor cap(1)In.
20. a kind of Optochemical sensor has as described in any one in claim 1-16
Measurement film(8)Or the sensor cap as described in any one in claim 17-19(1).
CN201410466339.0A 2013-09-12 2014-09-12 For photochemistry or the measurement film of amperometric sensor CN104458678B (en)

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